Citation: LIU Cheng-Yong, YAN Jian-Xin, LIN Yi-Ji, LI Dan, FANG Xue-Ming, ZHANG Hui. Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings[J]. Acta Physico-Chimica Sinica, ;2012, 28(02): 257-264. doi: 10.3866/PKU.WHXB201112091 shu

Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings

1.
State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Received Date: 28 September 2011
Available Online: 9 December 2011
Fund Project: 国家自然科学基金(20773098, 20973136)资助项目 (20773098, 20973136)

In order to explore the chiral origin of cis-[Ni(NCS)₂tren] [tren: tris(2-aminoethyl) amine], a pair of chiral crystals of cis-[Ni(NCS)₂tren] was characterized by X-ray single crystal structural analysis, solution UV-Vis-near infrared (NIR) spectroscopy, solid state UV-circular dichiroism (CD), and powder X-ray diffraction (XRD) spectra. The results indicated that the chiral crystals of cis-[Ni(NCS)₂tren] were obtained by mirror symmetry-breaking crystallization, and the special chiral ring conformations (δδλ, λλδ) of the coordinated tripod-type tren ligands are responsible for the chiral origin of cis-[Ni(NCS)₂tren]. The Cotton effects of Ni(II) complexes in the solid-state UV-CD spectra are presumably attributed to the π-π^* and charge-transfer chromophores of the NCS^- ligands by the chiral perturbation of the helical ring conformations and metal-centered chirality. According to the statistical results of solid-state CD spectra of cis-[Ni(NCS)₂tren] for twenty batch syntheses, their enantiomeric excess (ee) values are between 39% and 100%.
- Chirality,
- Mirror symmetry breaking,
- Ring conformational isomerism,
- Tris(2-aminoethyl)amine,
- Solid state CD spectroscopy
1. [1]
  (1) Santia , A.; Pere, A.; David, A. Chem. Soc. Rev. 2005, 34 (4), 313.
2. [2]
  (2) Brock, C. P.; Dunitz, J. D. Chem. Mater. 1994, 6 (8), 1187.
3. [3]
  (3) Nagasato, S., Katsuki, I.; Motoda, Y.; Sunatsuki, Y.; Matsumoto, N.; Kojima, M. Inorg. Chem. 2001, 40 (11), 2534.
4. [4]
  (4) Ikuko, K.; Naohide, M.; Masaaki, K. Inorg. Chem. 2000, 39 (15), 3350.
5. [5]
  (5) Katsuki, I.; Motoda, Y.; Sunatsuki, Y.; Matsumoto, N.; Nakashima, T.; Kojima, M. J. Am. Chem. Soc. 2002, 124 (4), 629.
6. [6]
  (6) Saha, M. K.; Fronczek, F. R.; Rees, L. H.; Bernal, I. Inorg. Chem . Commun. 2003, 6 (8), 983.
7. [7]
  (7) Rao, A. S.; Pal, A.; Ghosh, R.; Das, S. K. Inorg. Chem. 2009, 48 (5), 1802.
8. [8]
  (8) Purcell, K. F.; Kotz, J. C. Inorganic Chemistry;W. B. Saunders Company: Philadelphia, 1977; pp 642-644.
9. [9]
  (9) Mason S. F. Molecular Optical Activity and the Chiral Discriminations; Cambridge University Press: Cambridge, 1982; Chapter 7.
10. [10]
  (10) Zhang, H. Coordination Chemistry —Principles and Applications. Chemical Industry Press: Beijing, 2009. [章慧. 配位化学—原理与应用. 北京: 化学工业出版社, 2009.]
11. [11]
  (11) Jin, D. M.; ZhuW. X. Study Methods of Coordination Chemistry. Science Press: Beijing, 1996; Chapter 7. [金斗满, 朱文祥. 配位化学研究方法. 北京: 科学出版社, 1996: 第七章.]
12. [12]
  (12) Bosnich, B.; Harrowfield, J. M. J. Am. Chem. Soc. 1972, 94 (10), 3425.
13. [13]
  (13) Aoki, T.; Matsumoto, K.; Ooi, S.; Kuroya, H. Bull. Chem. Soc. Jpn. 1973, 46, 159.
14. [14]
  (14) Bernal, I. Inorg. Chim. Acta 1985, 96 (1), 99.
15. [15]
  (15) Bernal, I.; Cetrullo, J. Inorg. Chim. Acta 1988, 150 (1), 75.
16. [16]
  (16) Bernal, I.; Cetrullo, J. Inorg. Chem. 1993, 32 (19), 4098.
17. [17]
  (17) Bernal, I.; Cetrullo, J. J. Coord. Chem. 1993, 28 (1), 89.
18. [18]
  (18) Bernal, I.; Cetrullo, J.; Myrczek, J. J. Coord. Chem. 1993, 30 (1), 29.
19. [19]
  (19) Bernal, I.; Myrczek, J.; Cai, J. Polyhedron 1993, 12 (10), 1149.
20. [20]
  (20) Nakagawa, H.; Ohba, S.; Asakura, K.; Miura, T.; Tanaka, A.; Osanai, S. Acta Cryst. 1997, 53 (2), 216.
21. [21]
  (21) Gerard, K. J.; Morgan, J.; Steel, P. J.; House, D. A. Inorg. Chim. Acta 1997, 260 (1), 27.
22. [22]
  (22) Bernal, I.; Somoza, F.; Chen, Y. C.; Massoud, S. S. J. Coord. Chem. 1997, 41 (3), 233.
23. [23]
  (23) Bose, D.; Rahaman, S. H.; Ghosh, R.; Mostafa, G.; Ribas, J.; Hung, C. H.; Ghosh, B. K. Polyhedron 2006, 25 (3), 645.
24. [24]
  (24) Nie, F. M.; Dong, Z. Y. J. Chem. Crystallogr. 2011, 41 (1), 1.
25. [25]
  (25) Wang, Y.;Wang, Y. K.;Wang, J. M.; Liu, Y.; Yang, Y. T. J. Am. Chem. Soc. 2009, 131 (25), 8839.
26. [26]
  (26) Richardson, F. S. Chem. Rev. 1979, 79 (1), 17.
27. [27]
  (27) Okawa, H. Coord. Chem. Rev. 1988, 92, 1.
28. [28]
  (28) Ziegler, M.; von Zelewsky, A. Coord. Chem. Rev. 1998, 177 (1), 257.
29. [29]
  (29) Davis, A. V.; Fiedler, D.; Ziegler, M.; Terpin, A.; Raymond, K. N. J. Am. Chem. Soc. 2007, 129 (49), 15354.
30. [30]
  (30) Dwyer, F. P.; Garvan, F. L.; Shulman, A. J. Am. Chem. Soc. 1959, 81 (2), 290.
31. [31]
  (31) McCaffery, A. J.; Mason S. F.; Norman, B. J. Chem. Commun. 1965, No. 1, 49.
32. [32]
  (32) Bosnich, B.; Sullivan, E. A. Inorg. Chem. 1975, 14 (11), 2768.
33. [33]
  (33) Zhou, N.;Wan, S. G.; Zhao, J.; Lin, Y. J.; Xuan,W. M.; Fang, X. M.; Zhang, H. Science in China Series B : Chemistry 2009, 52 (11), 1851.
34. [34]
  (34) Lin, Y. J.;Wan, S. G.; Zou, F.;Wang, Y. K.; Zhang, H. New J. Chem. doi: 10.1039/C1NJ20430K.
35. [35]
  (35) Richard, M. H.; Rob, S. Inorg. Chem. 2009, 48 (21), 10476.
36. [36]
  (36) Ding, L.; Lin, L. R.; Liu, C. Y.; Li, H. K.; Qin, A. J.; Liu, Y.; Song, L.; Zhang, H.; Tang, B. Z.; Zhao, Y. F. New J. Chem. 2011, 35 (9), 1781.
37. [37]
  (37) Pescitelli, G.; Kurtán, T.; Florke, U.; Kröhn, K.; Krohn, K. Chirality 2009, 21 (1E), E181.
38. [38]
  (38) Kuroda, R.; Honma, T. Chirality 2000, 12 (6), 269.
39. [39]
  (39) Spitz, C.; Dähne, S. J. Phys. Chem. B 2000, 104 (36), 8664.
40. [40]
  (40) Castiglioni, E.; Biscarini, P.; Abbate, S. Chirality 2009, 21 (1E), E28.
41. [41]
  (41) Bilotti, I.; Biscarini, P.; Castiglioni, E.; Ferranti, F.; Kuroda, R. Chirality 2002, 14 (9), 750.
42. [42]
  (42) Minguet, M.; Amabilino, D. B.;Wurst, K.; Veciana, J. J. Chem. Soc. Perkin Trans 2 2001, 5, 670.
43. [43]
  (43) Zhang, H.; Chen, Y. C.;Wang, F.; Qiu, X. M.; Li, L.; Chen, J. G. Acta Phys. -Chim. Sin. 2006, 22 (6), 666. [章慧, 陈渊川, 王芳, 邱晓明, 李丽, 陈坚固. 物理化学学报, 2006, 22 (6), 666.]
44. [44]
  (44) Sheldrick, G. M. SHELXS97 and SHELXL97; University of Göttingen: Germany, 1997.
45. [45]
  (45) Farrugia, L. J. J . Appl . Cryst. 1999, 32, 837.
46. [46]
  (46) Farrugia, L. J. J . Appl . Cryst. 1997, 30, 657.
47. [47]
  (47) Wang, F.; Zhang, H.; Li, L.; Hao, H. Q.;Wang, X. Y.; Chen, J. G. Tetrahedron: Asymmetry 2006, 17 (14), 2059.
48. [48]
  (48) Lever, A. B. P. Inorganic Electronic Spectroscopy, 2nd ed.; Elsevier Science: New York, 1984; 507-520.
49. [49]
  (49) Lennartson, A.; Vestergren, M.; Hakansson, M. Chem. Eur. J. 2005, 11 (6), 1757.
1. [1]
  Qi Liang , Xinxin Wang , Xinmiao Zhao , Mohan Yu , Yue Sun . 电子圆二色谱结合量子化学计算的氨基酸手性解析——介绍一个计算化学综合实验. University Chemistry, 2026, 41(5): 380-390. doi: 10.12461/PKU.DXHX202511096
2. [2]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
3. [3]
  Guilan He , Yaofeng Yuan . 手性二茂铁双膦配体Xyliphos的合成及应用. University Chemistry, 2025, 40(8): 130-137. doi: 10.12461/PKU.DXHX202409122
4. [4]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
5. [5]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
6. [6]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
7. [7]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
8. [8]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
9. [9]
  Qiuting Zhang , Fan Wu , Jin Liu , Zian Lin . Chromatographic Stationary Phase and Chiral Separation Using Frame Materials. University Chemistry, 2025, 40(4): 291-298. doi: 10.12461/PKU.DXHX202405174
10. [10]
  Heyu Li , Lingjiao Li , Haiyu Wang , Bin Liu , Lianfen Chen , Zhiliang Jin . Chirality regulated CdS/Co-doped Ti₃C₂ MXene Schottky heterojunction for microplastic photoreforming to hydrogen and pyruvic acid. Acta Physico-Chimica Sinica, 2026, 42(10): 100350-0. doi: 10.1016/j.actphy.2026.100350
11. [11]
  Zhengjie Miao , Chuanqiang Zhou , Yuanyuan Ren , Xiangping Xu , Ju Xie , Jie Han . Hierarchical chiral nanoribbons of achiral oligoaniline: temperature induced helicity inversion and enantioselective crystallization application. Acta Physico-Chimica Sinica, 2026, 42(10): 100256-0. doi: 10.1016/j.actphy.2026.100256
12. [12]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
13. [13]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
14. [14]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
15. [15]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
16. [16]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . Performance and Electrochemical Asymmetry Optimization of Hydrogen Electrode Supported Reversible Solid Oxide Cell. Acta Physico-Chimica Sinica, 2025, 41(1): 100005-0. doi: 10.3866/PKU.WHXB202309037
17. [17]
  Xinhe Wu , Chang Cheng . Chiral COF-based S-scheme heterojunction for spin-polarized photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2026, 42(9): 100303-0. doi: 10.1016/j.actphy.2026.100303
18. [18]
  Wenliang Wang , Weina Wang , Tian Sheng , Nan Wei , Sufan Wang , Tao Zhou . 过渡金属/氧化物催化CO₂加H₂还原生成甲醇的甲酸盐与甲酰基路径的前线轨道对称性分析. University Chemistry, 2026, 41(9): 405-411. doi: 10.12461/PKU.DXHX202508059
19. [19]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
20. [20]
  Runjie Li , Hang Liu , Xisheng Wang , Wanqun Zhang , Wanqun Hu , Kaiping Yang , Qiang Zhou , Si Liu , Pingping Zhu , Wei Shao . 氨基酸的衍生及手性气相色谱分离创新实验. University Chemistry, 2025, 40(6): 286-295. doi: 10.12461/PKU.DXHX202407059

Get Citation

PDF

XML

Metrics

PDF Downloads(935)
Abstract views(2811)
HTML views(68)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Mirror Symmetry Breaking of cis-[Ni(NCS)2tren]: Special Chiral Conformations of Chelate Rings

Metrics

通讯作者: 陈斌, bchen63@163.com

Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings